Oxo process using mixture of alkenes and dienes



of equipment required processes.

United States Patent ()fiice 2,694,091 x0 PROCESS USING OF -ALKENES AND DIENES Philip Geoffrey Harvey and Norvik Ackroyd, Norton-on- Te'es, England, a's'signors "to Imperial Chemical Industries Limited, a corporation of Great Britain No Drawing. Application November 28, 1951, Serial N0. 258,753

Claims priority, application Great Britain September 12, 1949 '8 Claims. C1. nee-604 This invention relates to the production of oxygenated organic compounds and is a continuation-in-part of application Serial .No. 180,707., filed August 21, 1950, now abandoned.

:It has previously been common practice in the carbonyl'a'tio'n of olefines to employ a's carbonylating gas a mixture of carbon monoxide and hydrogen in which the molar ratio COZHz was 111 since this gives the stoichiometric proportions for'direct addition to the double bond, but gas of this composition has a strongly corrosive effect on ordinary steel equipment. When the attempt is made *to carbonylate olefines containing also diand/ or polyenes using less corrosive gas mixtures and a dissolved cobalt compound as catalyst it has now been found that carbonylation is inhibited, apparently owing 'to the presence of these last two classes of compounds. However, it has been found possible according to the present invention to carbonylate these diflicult mixtures by arranging to have ipresent initially an olefine substantially free from said diand poly-enes, preferably a substantially pure olefine, and using gas 'mixtures having compositions, and concentrations of dissolved cobalt compounds, all as hereinafter defined.

nomic in the sense that it gives high conversions and yields from these starting materials, which are so 'difiicult to carbonylate, and that the auxiliary olefine is itself c'arbonylated reaction vessel is achieved. This is especially 'so when the auxiliary olefine selected is one which car'bo'nylates at substantially the same rate as would 'the difiicult olefine if free from diand poly-ene. This aspect is important economically by reason of the high capital cost for superatmospheric pressure An additional advantage of the invention is that it permits the return of large quantities of hydrogen from the later carbonyl decomposition zone, and from the hydrogenation step to the carbonylation step and the use as feed gas in the last mentioned step of Water gas with a COIHz molar ratio of 1:1. This aitords considerable economy in the over-all process.

Furthermore, by using carbonylating gas having the low COzHz molar ratios claimed the need for costly CO-resistant apparatus is dispensed with. Besides, to the best of available knowledge, no one has been successful in continuously carbonylating olefines from cracked paraftins using the low COzHz ratios described in the present specification Without prior treatment of the olefine mixture.

According to the present invention there is provided a process of the Oxo-type for the production of organic oxygen containing compounds, especially aldehydes, by k the reaction in the liquid phase of olefines containing at least one alkene having at least 5 carbon atoms in the molecule together with at least one olefine selected from alicyclic and aliphatic di-enes and poly-enes under elevated pressure and temperature in the presence of a previously activated cobalt catalyst, characterised in that: first said catalyst is formed in alkene having at least 5 carbon atoms in the molecule and substantially free from inhibiting materials having dissolved therein at least 0.01%, preferably 0.1%, by weight of cobalt calculated and that, therefore, high output from the Moreover, the process of the present invention is eco- 2,694,091 Patented Nov. 9,1954

'as metal by introducing into "said a'lkene 'at elevated pressure and temperature a gas mixture comprising "carbon monoxide and hydrogen having 'a COIH'z molar ratio of at least 1 5, preferably at least 1:3, and in which the partial pressure of'carbon monoxide is at least 50 atmos- .pheres -until reaction is established and, thereafter, effectin'g carbonylation 'by introducing into the preformed catalyst solution at elevated temperature and pressure the "ol'efin'ic material and -'a gas mixture comprising carbon monoxide and "hydrogen in which the molar ratio CO:H2 is firo'm 3:7 to 2:3, while maintaining the cobalt concentration in the mixture at at least 0. 1% by weight, calculated as metal, by introduction of *a soluble "organic compound thereof in solution.

The use as catalyst of a soluble organic cobalt compound in solution aifords the advantages that it perm-its very accurate continuous control of cobalt concentration in the reaction space, which is of extreme importance in a sensitive process like the 0x0 process and that, in contrast to catalyst suspensions, the reaction mixture can be easily pumped and "erosion of valves and choking of lines can be substantially eliminated. The inhibiting effect "of diand/or poly e'nes is very marked when active "carbonylating catalyst is 'to be formed from dissolved organic cobalt compounds. Moreover, the ability to use with diilicul't alkene mixtures of this sort the low cobalt proportions specified, viz., 0.1%, results in considerable savings 'of this costly metal.

In order to keep corrosion to a minimum it is preferred to operate in the first "stage with a gas in which the molar ratio CQzHz does not exceed 2 3-.

Establishment of the main reaction is indicated by exotherm'icity-or fall of pressure.

The process of 'the invention is especially applicable to mixtures containing from C5 to 'C18 mono olefines, especially those containing -up to '12carbon atorr'rs. It is of marked value in relation to O5 olefines since these are most commonly obtained from cracking operations. Olefines produced by cracking may contain cyclic monoolefines in appreciable amounts. Because of its lower volatility it is preferred to use as auxiliary olefine one containing *at least 6 carbon atoms in the "molecule.

While the invention is :not to be considered as depending 'on any particular "theory, it is believed that diand poly-cites, -especially those which are conjugated, inhibit carbonylation.

Diand poly-ones are distinguished by having higher densities and refractive indices than the corresponding mono-olefines, and their presence is indicated by refractive index measurement, infra red spectroscopy, or density measurement.

Preferably the cobalt is employed as a soluble salt of an organic acid dissolved in the liquid feed or a part thereof, e. g., cobalt naphthenate or the acetate, laurate, hexahydrobenzoate or 3,5,5-trimethyl-hexoate. also be introduced as a solution in an inert medium, e. g., the hydrogenated alcohol product.

The invention is of particular value in relation to the production of aldehydes from C6 to Cs alkene mixtures, e. g., those containing alpha-olefines, obtained by the thermal cracking of higher hydrocarbons, e. g., paraflin waxes. Suitable temperatures are, for example l30190 C., preferably 175 C., and a pressure of carbonylating gas of 200300 atmospheres gauge, preferably 250 atmospheres.

The aldehydes produced by the process can be readily hydrogenated to alcohols at snperatmospheric temperatures and pressures, e. g., 250 and 150 atmospheres gauge, using Cu or Ni catalysts. Copper-on-zinc oxide and copper-on-chromia are especially suitable catalysts for the hydrogenation step.

The process is illustrated by the following example.

Example (i) Operating according to the prior art process pure di-isobutene containing 0.1% of cobalt as naphthenate was fed to a reaction zone at C. and 250 atmospheres pressure together with a mixture of carbon monoxide and hydrogen in which the molar ratio carbon monoxidezhydrogen was 1:3 in the proportion of 1000 cubic metres of free gas per cubic metre of di-isobutene,

It may the liquid space velocity being 0.5 litre per litre of free reaction space per hour. Carbonylation was initiated immediately and there were obtained oxygenated organic compounds containing 3,5,5-trimethyl hexanal. When the inlet gas was cut off the reaction ceased, but re-started immediately on re-introduction of the carbonylating gas.

(ii) The process was repeated under the same conditions as given in paragraph (i) except that the di-isobutene feed was replaced by di-isobutene containing of cyclopentadiene. After passing the same carbonylatlng gas for 2 hours it was found that no carbonylation had occurred.

(iii) Operation according to the process of the present invention will now be described using an alkene feed which trial showed could not be carbonylated under the conditions described in paragraphs (i) and (ii) above. A reactor is filled initially with di-isobutene containing 0.1% by weight of cobalt as the naphthenate and the whole is treated at 250 atmospheres gauge pressure and 140 to 160 C. with a mixed gas comprising 30% CO and 70% H2, when reaction to oxygenated products occurs. Liquid di-isobutene containing the above catalyst is fed continuously at a liquid space velocity of 0.5 litre/litre/hour to the reactor for a period of 1 to 2 hours when the liquid feed stream is changed to a mixture of Ca to Ca alkenes, produced by the thermal cracking of parafiin Wax, containing 0.1% by weight of cobalt dissolved therein as naphthenate and this is fed continuously to the reactor at the above liquid space velocity. Treatment of this feed at 150 to 170 C. and 250 atmospheres gauge pressure with a gas of the above composition at a gaszliquid ratio of 1000 cubic metres/cubic metre results in a pass conversion to oxygenated products of about 80% calculated on the alkene feed.

Operating according to the process of the invention the main end products, obtained after hydrogenation of the carbonylation product, from C1; normal olefines are the normal C1t+1 alcohol and the 2-methyl-Cn alcohol (where n=the number of carbon atoms). Thus normal heptanol and Z-methyl hexanol are obtained from normal hexene, and the corresponding normal and Z-methyl alcohols from normal heptane and octene. Other isomeric alcohols are also produced in minor amounts.

We claim:

1. A continuous process for the production of organic oxygen-containing compounds by carbonylating a mixture containing at least one alkene having at least five carbon atoms in the molecule together with at least one di-ene selected from the group consisting of aliphatic and alicyclic di-enes which comprises forming an activated cobalt catalyst by contacting in the liquid phase at elevated temperature and pressure a small proportion i at least 0.01% by weight of cobalt, calculated as metal,

in solution as an organic compound in a mixture of alkenes having at least five carbon atoms in the molecule and substantially free from inhibiting materials with carbon monoxide and hydrogen in which the molar ratio of COzHz is at least 1:5 and in which the partial pressure of carbon monoxide is at least 50 atmospheres, until carbonylation reaction is established, and thereafter effecting carbonylation of said alkene mixture containlng at least one di-ene by introducing said last named alkene mixture into the preformed catalyst solution, and reacting the mixture so formed in the liquid phase at elevated temperature and pressure with carbon monoxide and hydrogen in which the molar ratio of COzHz is from 3:7 to 2:3, the concentration of cobalt in the mixture so formed being maintained in small concentration not less than 0.1% by weight of cobalt, calculated as metal, by introducing a soluble organic compound of cobalt in solution into the mixture so formed.

2. A process as claimed in claim 1 in which a portion of the olefines selected from the group consisting of aliphatic and alicyclic di-enes are conjugated.

3. A process as claimed in claim 1 in which the alkene used initially has at least 6 carbon atoms in the molecule.

4. A process as claimed in claim 1 in which the concentration of cobalt present in dissolved form in the first stage is at least 0.1% by weight, calculated as metal, of the liquid mixture.

5. A process as claimed in claim 1 in which the organic cobalt compound is the salt of a carboxylic acid.

6. A process as claimed in claim 1 in which the molar ratio, COzHz, of the gas used in forming the activated cobalt catalyst is up to 2:3.

7. A process as claimed in claim 1 in which the alkene mixture comprises C6 to Ca alkenes obtained by thermal cracking of higher hydrocarbons and in which a temperature of to C. and a pressure of 200 to 300 atmospheres gauge are employed.

8. A process as claimed in claim 1 in which the molar ratio CO:H2 in the gaseous mixture employed in forming the activated cobalt catalyst is at least 1:3.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,437,600 Gresham et al Mar. 9, 1948 2,477,554 McKeever July 26, 1949 2,497,303 Gresham et al Feb. 14, 1950 2,587,858 Keulemans Mar. 4, 1952 2,647,149 Condit et al. July 28, 1953 

1. A CONTINUOUS PROCESS FOR THE PRODUCTION OF ORGANIC OXYGEN-CONTAINING COMPOUNDS BY CARBONYLATING A MIXTURE CONTAINING AT LEAST ONE ALKENE HAVING AT LEAST FIVE CARBON ATOMS IN THE MOLECULE TOGETHER WITH AT LEAST ONE DI-ENE SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC AND ALICYCLIC DI-ENES WHICH COMPRISES FORMING AN ACTIVATED COBALT CATALYST BY CONTACTING IN THE LIQUID PHASE AT ELEVATED TEMPERATURE AND PRESSURE A SMALL PROPORTION AT LEAST 0.01% BY WEIGHT OF COBALT, CALCULATED AS METAL, IN SOLUTION AS AN ORGANIC COMPOUND IN A MIXTURE OF ALKENES HAVING AT LEAST FIVE CARBON ATOMS IN THE MOLECULE AND SUBSTANTIALLY FREE FROM INHIBITING MATERIALS WITH CARBON MONOXIDE AND HYDROGEN IN WHICH THE MOLAR RATIO OF CO:H2 IS AT LEAST 1:5 AND IN WHICH THE PARTIAL PRESSURE OF CARBON MONOXIDE IS AT LEAST 50 ATMOSPHERES, UNTIL CARBONYLATION REACTION IS ESTABLISHED, AND THEREAFTER EFFECTING CARBONYLATION OF SAID ALKENE MIXTURE CONTAINING AT LEAST ONE DI-ENE BY INTRODUCING SAID LAST NAMED ALKENE MIXTURE INTO THE PREFORMED CATALYST SOLUTION, AND REACTING THE MIXTURE SO FORMED IN THE LIQUID PHASE AT ELEVATED TEMPERATURE AND PRESSURE WITH CARBON MONOXIDE AND HYDROGEN IN WHICH THE MOLAR RATIO OF CO:H2 IS FROM 3:7 TO 2:3 THE CONCENTRATION OF COBALT IN THE MIXTURE SO FORMED BEING MAINTAINED IN SMALL CONCENTRATION NOT LESS THAN 0.1% BY WEIGHT OF COBALT, CALCULATED AS METAL BY INTRODUCING A SOLUBLE ORGANIC COMPOUND OF COBALT IN SOLUTION INTO THE MIXTURE SO FORMED. 